Schiff{3 s base dichloroacetamides

ABSTRACT

IN WHICH R1 is selected from the group consisting of alkenyl, alkyl, alkynyl and alkoxyalkyl; and R2 is selected from the group consisting of alkenyl-1, lower alkylimino, cyclohexenyl-1 and lower alkyl substituted cyclohexenyl-1. The compounds of this invention are useful as herbicidal antidotes.   Schiff&#39;&#39;s base dichloroacetamides having the formula

United States Patent 1 Baker Feb. 18, 1975 SCHIFFS BASEDICHLOROACETAMIDES [75] Inventor: Don R. Baker, Orinda, Calif.

[73] Assignee: Stauffer Chemical Company,

Westport, Conn [22] Filed: July 17, 1972 [21] Appl. No.: 272,271

[52] US. Cl. 260/561 HL, 71/118, 260/561 H, 260/566 B, 260/566 R [51]Int. Cl. C07c 103/30 [58] Field of Search 260/561 l-lL [56] ReferencesCited OTHER PUBLICATIONS Primary ExaminerLewis Gotts AssistantExaminer-Ethel G. Love Attorney, Agent, or Firm-Harry A. Pacini; DanielC. Block; Edwin H. Baker ABSTRACT Schiffs base dichloroacetamides havingthe formula 9 itcc1 -c-N 1 in which R is selected from the groupconsisting of alkenyl, alkyl, alkynyl and alkoxyalkyl; and R is selectedfrom the group consisting of alkenyl-l, lower alkylimino, cyclohexenyl-land lower alkyl substituted cyclohexenyl-l. The compounds of thisinvention are useful as herbicidal antidotes.

14 Claims, N0 Drawings 1 SCHIFFS BASE DICHLOROACETAMIDES DESCRIPTION OFTHE INVENTION In the above description, the following preferredembodiments are intended for'the various substituent groups: alkylpreferably includes those members having from 1 to 6 carbon atoms inboth straight chain and branched chain configurations, for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, 1,1-dimethylbutyl, n-hexyl and the like; alkenyl preferably includes thosemembers in both straight chain and branched chain configurations havingat least one double bond and from 3 to 6 carbon atoms, inclusive alkynylpreferably includes those members in both straight chain and branchedchain configurations having at least one triple bond and from 3 to 6carbon atoms, inclusive; lower alkyl preferably includes those membershaving from I to 4 carbon atoms, inclusive, in both straight chain andbranched chain configurations for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec.-butyl and the like.

The compounds of the present invention are prepared by several differentmethods, depending upon the nature of the starting materials and theproducts desired. The non-hydrazide compositions are prepared by thedisplacement and rearrangement reaction between an appropriate Schiffsbase and an acid chloride, di-

chloroacetyl chloride. The Schiffs base is the product of a primaryamine with a carbonyl-containing compound, such as a ketone or aldehyde.The hydrazidecontaining compositions are prepared by the reactionbetween an acid chloride, dichloroacetyl chloride and an alkylhydrazone. The reactions proceed readily in the liquid phase. Theemployment of a solvent is useful, although unnecessary. Such solventsas diethyl ether and the like, facilitate processing of the reactionproduct. The reactions are carried out at temperatures which permitoperation in the liquid phase. The preferable temperatures are betweenabout room temperature and reflux temperature of the solvent, if asolvent is employed. In each instance after the reaction is complete,the recovery of the product is carried out by normal work-up proceduressuch as crystallization, sublimation or distillation.

2 The compounds of the present invention and their preparation are moreparticularly illustrated by the following examples. Following theexamples is a table of compounds which are prepared according to theprocedures described herein.

EXAMPLE I Preparation of N-allyl N-( l-hexenyl )-dichloroacetamidePreparation of Intermediate: N-cyclohexylidene allylamine. Cyclohexanone(52 ml.) was added over a period of about-20 minutes to a stirred andcooled solution of allylamine (38 ml., 0.50 mole) in 100 ml. diethylether. The reaction mixture was stirred for about 20 minutes at roomtemperature. Potassium hydroxide pellets (17 g.) were added to themixture and then heated to reflux (45C.) with stirring for about 30minutes. The resulting layers were separated and the organic layer wasdried over sodium carbonate. The organic solvent was evaporated invacuo. There was obtained 55 g. of the intermediate, an oil.

Dichloroacetyl chloride (4.8 ml., 0.05 mole) was added to a solution ofN-cyclohexylidene allylamine (0.6 g.) in ml. of diethyl ether and 7.0ml. triethylamine. During the addition, the reaction mixture was cooled.After standing for about 16 to l8hours, the reaction mixture was washedwith two 100 ml. portions of water. Magnesium sulfate was added duringthe last wash to aid phase separation. The resulting organic solutionwas dried over magnesium sulfate. Upon evaporation in vacuo of theorganic solvent, there was obtained 12.4 g. of the title compound, anoil, n 1.5093.

EXAMPLE II Preparation of N-t-butyl N-( l-butenyl )-dichloroacetamide Ina similar procedure as Example I, 6.6 g. (0.052 mole)N-butylidene-t-butylamine was reacted with 4.8 ml. (0.05 mole)dichloroacetylchloride in 100 ml. diethyl ether and'7.2 ml.triethylamine. There was obtained 9.3 g. of the title compound, an oil,r1 1.4858.

EXAMPLE III Preparation of N-ethyl N-( 3-pent-3-enyl )-dichloroacetamideIn a similar procedure as Example I, 5.9 g. (0.052 mole) N-3-pentylideneethylamine was reacted with 4.8 ml. (0.05 mole) dichloroacetyl chloridein 100 ml. diethyl ether and 7.2 ml. triethylamine. There was obtained7.7 g. of the title compound, an oil, u 1.4826.

EXAMPLE IV Preparation of Acetone N-methyl dichloroacethydrazidePreparation of Intermediate: Acetone N-methyl hydrazide. Acetone (72ml.) was added to a stirred and cooled solution of methyl hydrazine (46g., 1.00 mole) in 100 ml. benzene and 1 ml. glacial acetic acid. Afterthe addition was complete, the solution was heated to reflux and 21 ml.ofaqueous solution was removed as benzene-water azeotripe. The reactionsolution was cooled and filtered through a bed of sodium carbonate andconcentrated by removal of solvent in vacuo.

There was obtained a yield of 80 g. of the title intermediate, an oil.The structure was confirmed by nuclear magnetic resonance, which alsoindicated about 21 mole per cent benzene also present.

To prepare the title compound, 4.8 ml. (0.05 mole) dichloroacetylchloride was added to a solution of acetone N-methyl hydrazide (5.5 g.,0.05 mole) in 100 ml. diethyl ether and 7.2 ml. triethylamine. Thereaction mixture was stirred and cooled during the addition. Afterstanding for about one hour the reaction mixture was washed with two 100ml. portions of water and dried over magnesium sulfate. The solvent wasevaporated in vacuo to yield 5.0 g. of the title compound, an oil, n1.5046.

Other compounds were prepared in analogous reactions employing theappropriate starting materials as outlined above. The following is atable of Compounds representative of those embodied by the presentinvention. Compound numbers have beenassigned to them and are used foridentification throughout the balance of the specification.

reached a relatively high degree of commercial success. These herbicidesare immediately toxic to a large number of weed pests, both broadleafand grasses. at different concentrations varying with the resistance ofthe weeds to be controlled. Some examples of these compounds aredescribed and claimed in U.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897,3,185,720 and 3,198,786.

It has been found in practice that the use of the thiocarbamate-typeherbicides, when employed as an herbicide in corn fields, sometimescauses serious injury to the corn plants. Various unfavorable effectscan be noted. For example, when used in the recommended amounts in thesoil to control many broadleaf and grass weeds, serious malformation andstunting of the corn plants result. This abnormal growth in the cornplants is undesirable and results in loss of crop yield.

It is clear that the classes of herbicidal agents described andillustrated herein are characterized as effective herbicides exhibitingsuch activity. The degree ii /R 2 accl c R coumrmn 30 man 1 2 11 1 caca=cn 0 1.5093

, 3 0 (CH3) 2C 1 CH -CH=CHCH2CH3 semisoli d 5 cu ca czn cn -ca=caca cn 1.4930

cu cu cn -c'(cu )==cnc1r cn 1.5046 s ca -N=c(cn 1.5046

. CH 10 cu cn cn ocmca 2 {j The compounds of this invention have beenfound to be active as effective protectants or antidotes against 5injury by thiocarbamateherbicides to various beneficial plants,especially corn.

Among the many herbicidal compounds commercially available, thethiocarbamate herbicides alone or mixed with other herbicides such as triaz i r 1 e s have of this herbicidal activity varies among specificcom- I plant species readily may be made. Within the present inventionthe prevention of injury to a desired crop species in the presence of aspecific compound or combination may be achieved. The beneficial plantspecies which can be protected by this method is not intended to belimited by the specific crops employed in the examples.

The herbicidal compounds employed in the method of this invention areactive herbicides of a general type. That is, the members of the classesare herbicidally effective against a wide range of plant species with nodiscrimination between desirable and undesirable species. The method ofcontrolling vegetation comprises applying an herbicidally effectiveamount of the herein described herbicidal compounds to the area or plantlocus where control is desired.

An herbicide is used herein means a compound which controls or modifiesthe growth of vegetation or plants. Such controlling or modifyingeffects include all deviations from natural development; for example,killing, retardation, defoliation, desiccation, regulation, stunting,tillering, stimulation, dwarfing and the like. By plants, it is meantgerminant seeds, emerging seedlings, and established vegetation,including the roots and above-ground portions.

The herbicidal active compositions and utility of this inventioncomprising thiocarbamates in combination with antidote compoundsdescribed hereinabove were tested in the following manner.

Corn Seed Treatment Flats were filed with Felton loamy sand soil. Soilincorporated herbicides were applied at this time. The

soil from each flat was placed into a five-gallon cement mixer where thesoil was mixed as the herbicides were applied using a predeterminedamount of a stock solution containing 936 mg. of 75.5% active ingredientto 100 ml. of water. One ml. of stock solution was applied to the soilin a volumetric pipet for each pound of herbicide desired. One ml. ofstock solution contains 7 mg. of herbicide which equals one pound peracre when applied to the soil in the flats. After the herbicideincorporation, the soil was placed back into the flats.

Flats of herbicide-treated and untreated soil were.

then ready to be planted. A pint sample of soil was removed from eachflat and placed next to each flat for later use in covering up theseeds. The soil was leveled and rows one-half inch deep were made forplanting seeds. Alternating rows of treated and untreated crop seedswere sown. In each test, six PAG 344T field corn seeds were planted ineach row. Rows were approximately 1% inches apart in the flat. Seedswere treated,

by placing 50 mg. of the antidote compound with 10 grams of corn seed ina suitable container and shaking them until the seeds were uniformlycovered with the compound. Antidote compounds also were applied asliquid slurries and powders or dusts. In some cases, we tone was used todissolve powdered or solid compounds so they could be more effectivelyapplied to the seeds.

After the flats were seeded, they were covered with the one pint of soilwhich had been removed just prior to planting. Flats were placed ongreenhouse benches where temperatures ranged from 7090C. Flats werewatered by sprinkling as needed to assure good plant growth. Per centcontrol ratings were taken two to four weeks after the treatments wereapplied.

In each test, the herbicide was applied alone, in combination with theseed protectant, and the seed protectant is applied alone to check forphytotoxicity. Untreated seeds were planted in adjacent rows to test forlateral displacement through the soil of the candidate compounds andpossible beneficial effect. The degree of the effect was noted bycomparison with the control. 1

v The results of these tests are tabulated in Table II.

TABLE II Percent Injury to Corn from EPTC* MF Malformation ST StuntingEPTC S-e\hyI-dipropylthiocarbamate Rating 2 weeks Multicrop AntidoteIncorporation Screen Plastic flats measuring 6 X 9.5 X 3 inches werefilled with 7 lb. of Felton loamy sand soil. EPTC was incorporated at 5lb/A, while a constant rate of 5 lb/A of the additive was used. EPTC andthe herbicide additive were applied separately by pipetting measuredamounts of the appropriate stock solutions into the soil duringincorporation in a 5 gallon rotary cement mixer. Stock solution for EPTCwas prepared as follows: 6700 mg. of EPTC 6E (75.5%) was diluted with500 ml. of deionized water so that 2 ml. equals 5 lb/A/plastic flat.

Additive stock solutions were prepared'by diluting I02 mg. of technicalmaterial with 10 ml. of acetone 1% Tween 20 so that 2 ml. equals 5lb/A/plastic flat.

After the soil was treated with both herbicide and additive the soil wastransferred from the mixer back into the plastic flat where it was thenprepared for seeding. The initial step in preparation was to remove aone pint sample of soil from each flat to be retained and used to coverthe seeds after planting. The soil was then leveled and rows one-quarterinch deep were made in each flat. Flats treated with 5 lb/A of EPTC wereseeded to De- Kalb XL-44 corn (Zea maize), US H9 sugarbeets (Betavulgare), small seeded gray striped sunflower (Helianthus annus), Acalacotton (Gossypium hirsutum), Brag soybeans (Glycine max) and oilseedrape (Brassica napus). Seeds were then covered with the pint soil sampleremoved prior to seeding. The flats were then placed on greenhousebenches where temperatures were maintained between 90F. The soil was watered by sprinkling to assure good plant growth.

Injury ratings were taken 2 and 4 weeks after the treatments wereapplied. Soil treated with EPTC alone at one-half or 5 lb/A was includedto provide a basis for determining the amount of injury reductionprovided by the herbicide antidotes.

With Compound No. 10, after 2 weeks a difference in the amount of injurywas observed with the sun-' flower plants. Whereas all other cropsexhibited substantially the same amount of injury as those planted inEPTC treated soil, the sunflower plants in this test were substantiallyuninjured. After 4 weeks, the sunflower plants remained normal. After 4weeks, the corn plants were able to recover such that only about 60%injury was observed. The remaining crops at 4 weeks continued to showsubstantially identical injury as plants in the EPTC treated flats.

The antidote compounds of the present invention can be used in anyconvenient form. Thus, the antidote compounds can be made intoemulsifiable liquids, emulsifiable concentrates, liquid, wettablepowder, powders, granular or any other convenient form. In its preferredform, the antidote compounds are admixed with the thiocarbamates andincorporated into the soil prior to or after planting the seed. It is tobe understood, however, that the thiocarbamate herbicide can beincorporated into the soil and thereafter the antidote compound can beincorporated into the soil. Moreover, the seed can be treated with theantidote compound and planted into the soil which has been treated withherbicides or untreated with the herbicide and subsequently treated withthe herbicide. The addition of the antidote compound does not affect theherbicidal activity of the carbamate compounds.

The amount of the antidote composition present can range between about0.01 to about parts by weight per each part by weight of thiocarbamateherbicide. The exact amount of antidote compound will usually bedetermined on economic ratios for the most effective amount usable.

What is claimed is:

l. A compound having the formula n R H0012 c N\R ll R HCCl -c- 2 2 N Rlin which R, is alkyl having from 1 to 6 carbon atoms, inclusive, and Ris alkenyl-1 having from 3 to 6 carbon atoms, inclusive.

4. A compound according to claim 3 in which R, is tertiary-butyl and Ris butenyl-l.

5. A compound according to claim 3 in which R, is ethyl and R is l-ethylpropenyl-l.

6. A compound according to claim 3 in which R, is n-butyl and R isbutenyl-l.

7. A compound according to claim 3 in which R, is n-propyl and R isl-methyl butenyl-l.

8. A compound having the formula in which R, is alkynyl having 3 to 6carbon atoms, inclusive, and R is alkenyl-l having from 3 to 6 carbonatoms, inclusivc.

9. A compound according to claim 8 in which R, is 2-methyl-2-but-3-ynand R is butenyl-l.

10. A compound having the formula in which R, is alkyl having from i to6 carbon atoms, inclusive, and R is cyclohexenyl-l.

11. A compound according to claim 10 in which R, is n-propyl.

12. A compound having the formula R R HCCl -c-N 2 2 \R1 in which R, isalkoxyalkyl having a total of from 2 to 8 carbon atoms, inclusive, and Ris lower alkyl substituted cyclohexenyl-l, wherein said lower alkyl hasfrom 1 to 4 carbon atoms, inclusive.

1. A COMPOUND HAVING THE FORMULA
 2. A compound according to claim 1 inwhich R1 is allyl.
 3. A compound having the formula
 4. A compoundaccording to claim 3 in which R1 is tertiary-butyl and R2 is butenyl-1.5. A compound according to claim 3 in which R1 is ethyl and R2 is1-ethyl propenyl-1.
 6. A compound according to claim 3 in which R1 isn-butyl and R2 is butenyl-1.
 7. A compound according to claim 3 in whichR1 is n-propyl and R2 is 1-methyl butenyl-1.
 8. A compound having theformula
 9. A compound according to claim 8 in which R1 is2-methyl-2-but-3-yn and R2 is butenyl-1.
 10. A compound having theformula
 11. A compound according to claim 10 in which R1 is n-propyl.12. A compound having the formula
 13. A compound according to claim 12in which R1 is methoxyethyl and R2 is 3,5-dimethylcyclohexenyl-1.
 14. Acompound according to claim 12 in which R1 is isopropoxy-n-propyl and R2is 2,6-dimethylcyclohexenyl-1.